MOLECULAR ENERGY LEVELS DR IMRANA ASHRAF OUTLINE q MOLECULE q - - PowerPoint PPT Presentation

MOLECULAR ENERGY LEVELS

DR IMRANA ASHRAF

OUTLINE

q MOLECULE

q MOLECULAR ORBITAL THEORY q MOLECULAR TRANSITIONS q INTERACTION OF RADIATION WITH MATTER q TYPES OF MOLECULAR ENERGY LEVELS

q MOLECULE

q In nature there exist 92 different elements that correspond to stable atoms. q These atoms can form larger entities- called molecules. q The number of atoms in a molecule vary from two - as in N2 - to many thousand as in DNA, protiens etc. q Molecules form when the total energy of the electrons is lower in the molecule than in individual atoms. q The reason comes from the Aufbau principle - to put electrons into the lowest energy configuration in atoms. q The same principle goes for molecules.

q MOLECULE

q Properties of molecules depend on: § The specific kind of atoms they are composed of. § The spatial structure of the molecules - the way in which the atoms are arranged within the molecule. § The binding energy of atoms or atomic groups in the molecule.

TYPES OF MOLECULES

q MONOATOMIC MOLECULES

§ The elements that do not have tendency to form molecules. § Elements which are stable single atom molecules are the noble gases : helium, neon, argon, krypton, xenon and radon.

q DIATOMIC MOLECULES

§ Diatomic molecules are composed of only two atoms - of the same or different elements. § Examples: hydrogen (H2), oxygen (O2), carbon monoxide (CO), nitric oxide (NO)

q POLYATOMIC MOLECULES

§ Polyatomic molecules consist of a stable system comprising three or more atoms.

TYPES OF MOLECULES

q Empirical, Molecular And Structural Formulas

q Empirical formula: Indicates the simplest whole number ratio of all the atoms in a molecule. The empirical formula of glucose is CH2O. q Molecular formula: Describes the exact number and type of atoms in a single molecule of a compound. The molecular formula for glucose is C6H12O6 q Structural formula: Indicates not only the number of atoms but also their arrangement in space.

Formulas

Difference between Isomers and Allotrope

ISOTOPE Atoms with the same number of protons but different number of neutrons are called isotopes. By changing the number of neutrons, isotopes still maintain the same overall neutrality and hence the chemical behavior remains unchanged. ISOMERS Isomers are two molecules with the same atoms joined together in a different

• shape. They have same molecular formula but different chemical structure. For

example : Butane and isobutane ALLOTROPE They are different structural forms of the same element but can exhibit quite different physical and chemical properties. For example, carbon, diamond, graphite…

Examples of isomers and allotrope

Structural Isomers: same molecular formula but different structural formula Allotropes of carbon:

Diamond and graphite are two allotropes of carbon: pure forms of the same element that differ in structure.

Molecular Spectroscopy

Molecular spectroscopy : is the study of the interaction of electromagnetic (EM) radiation with matter. q Based on the analysis of EM radiation that is emitted, absorbed, or scattered by molecules- we can have information on q Chemical analysis q Molecular structure (bond lengths, angles, strengths, energy levels, etc...)

Energy Levels

• A quantum mechanical system or particle that is bound—that is, confined

spatially —can only take on certain discrete values of energy- called energy levels.

• The term is commonly used for the energy levels of electrons in atoms,

ions or molecules- which are bound by the electric field of the nucleus.

• Can also refer to energy levels of nuclei or vibrational or rotational energy

levels in molecules.

Ground and excited states

• If an atom, ion, or molecule is at the lowest possible energy level,

it and its electrons are said to be in the ground state.

• If it is at a higher energy level, it is said to be excited, or any

electrons that have higher energy than the ground state are excited.

• If more than one quantum mechanical state is at the same energy,

the energy levels are called degenerate energy levels.

Chemical Bonds

• Chemical bonds between atoms in a molecule form because they make the

situation more stable for the involved atoms.

• Covalent bond:, involves the sharing of electron pairs between atom.
• As atoms approach each other to covalently bond -their orbitals affect each
• ther's energy levels to form bonding and anti-bonding molecular orbitals.
• The energy level of the bonding orbitals is lower, and the energy level of the

anti-bonding orbitals is higher.

• For the bond in the molecule to be stable - the covalent bonding electrons
• ccupy the lower energy bonding orbital - which may be signified by such

symbols as σ or π.

q Molecular Orbital Theory

q Orbitals of individual atoms interact to produce new orbitals - called molecular orbitals Φ is the molecular orbital, φ is an atomic orbital and a is a coefficient Molecules have discrete energy levels - no continuum between levels. Absorbs electromagnetic radiation when the energy of photon corresponds to the difference in energy between two states.

1 N i i i

aϕ

=

Φ = ∑

q Molecular Energy Levles

Energy can be stored either as potential energy or kinetic energy, in a variety of ways including

• Translational energy: small amounts of energy stored as kinetic energy.
• Rotational energy: kinetic energy associated with the rotational motion
• f molecules.
• Vibrational energy: the oscillatory motion of atoms or groups of atoms

within a molecule (potential energy ↔ kinetic energy exchange).

• Electronic energy: energy stored as potential energy in excited

electronic configurations. All except the Translational energy are quantized Emolecule = Erotational + Evibrational + Eelectronic

q Molecular Transitions

Atomic and molecular vibrations correspond to excited energy levels in quantum mechanics

⇔

Energy Ground level Excited level

ΔE = hν

The atom is at least partially in an excited state. The atom is vibrating at frequency, ν.

q For a given frequency only one value of quantum energy for the photon is possible q Transitions between energy levels occur by absorption, emission and stimulated emission of photons

q Spontaneous Emission

q When an atom/ molecule in an excited state falls to a lower energy level - it emits a photon q Molecules typically remain excited for a few nanoseconds- upon de-excitation emit a photon of light. q This process is called fluorescence . Energy Ground level Excited level

Stimulated Absorption

q Atoms and molecules can also absorb photons, making a transition from a lower level to a more excited one

q Stimulated Emission

In 1916, Einstein showed another process called stimulated emission can also occur

q Molecular Trnasitions

Before After Absorption Stimulated emission Spontaneous emission

Electromagnetic radiation

q Electromagnetic (EM) radiation consists of photons which behave as both particles and waves.

• λ
• ν
• c = speed of light (2.998x108 ms-1)

λ = wavelength (m) ν = frequency (s-1) = wavenumber (m-1)

Electromagnetic spectrum

• Radio → nuclear spin in magnetic field
• Microwave → rotation
• Infrared → vibration
• Ultraviolet → electronic

Wavelength, λ

• μ

Frequency, ν

q INTERACTION OF RADIATION WITH MATTER

there are no available antized energy levels tching to the quantum ergy of the incident diation, then the m a t e r i a l w i l l b e ansparent to that diation

Wavelength

q X-RAY INTERACTIONS

Quantum energies of x-ray photons are too high to be absorbed by electronic transitions in most atoms -

• nly possibility is complete removal of an electron

from an atom - x-rays are ionizing radiation Photoionization: If all the energy is given to an electron Compton scattering: If part of the energy is given to an electron and the rest to a lower energy photon

q UlTRAVIOLET INTERACTIONS

Near UV radiation is absorbed very strongly in the surface layer of the skin by electron transitions At higher energies, ionization limit for many molecules are reached and the more dangerous photoionization processes occur. Sunburn is primarily an effect of UV radiation, and ionization produces the risk

• f skin cancer

q VISIBLE LIGHT INTERACTIONS

q Visible light is also absorbed by electron transitions q Higher energies are absorbed more relative to low energies - red light is less strongly absorbed than blue light q Absorption of visible light causes heating, but not ionization q Car windshields transmit visible light but absorb higher UV frequencies

q INFRARED (IR) INTERACTIONS

The energy level of infrared light corresponds to the energy required to cause molecular vibrations Vibrations arise as molecular bonds are not rigid but behave like springs

q INFRARED (IR) INTERACTIONS _ CONT’D

Vibrational transitions are Sub-divided into two classes: Stretching : symmetric and asymmetric Bending: scissoring, rocking, wagging and twisting Stretching frequencies are higher than corresponding bending frequencies - it i easier to bend a bond than to stretch or compress it Bonds to hydrogen have higher stretching frequencies than those to heavier atoms. Triple bonds have higher stretching frequencies than corresponding double bon

• which in turn have higher frequencies than single bonds

q MICROWAVE INTERACTIONS

q Quantum energy of microwave photons ( 10-5-10-3 eV) matches the ranges of energies separating quantum states of molecular rotations. q Like electronic and vibrational transitions rotational motion of molecules is quantized q Absorption of microwave radiation causes heating due to increased molecular rotational activity q Most matter transparent to µ-waves, microwave ovens use high intensity µ-waves to heat material

q MOLECULAR ENERGY LEVELS

q MOLECULAR ENERGY LEVELS _ CONT’D

Radiation can be absorbed

• r emitted if the molecule

changes any of its energy states.

q MOLECULAR ENERGY LEVELS _ CONT’D

The relative energy of the spacings between energy levels for various types of transitions in a molecule are in the order: The various types of energy transitions occur in different regions of the EM- spectrum and do not overlap

Rotational Transition 1-20 cm-1 Vibrational Transition 2000-4000 cm-1 Electronic Transition 10000-50000 cm-1

<< <<

q MOLECULAR ENERGY LEVELS _ CONT’D

Rotational Transition 1-20 cm-1 Microwave Vibrational Transition 2000-4000 cm-1 Infrared Electronic Transition 10000-50000 cm-1 UV-Visible

q ABSORPTION SPECTRA OF MOLECULES _ CONT’D

q Electronic, vibrational and rotational energy levels are superimposed q The absorption spectrum of a molecule is determined by all allowed transitions between pairs of energy levels that interact with the radiation field

V = Vibrational quantum number J = Rotational quantum number

VIBRATIONAL MOLECULAR LEVELS

q Like atoms - molecular motion is governed by quantum mechanics. q Chemical bond acts like a spring and can display Simple harmonic motion q Energies due to vibration are quantized : Eν = ħω (ν + ½) q Vibrational quantum number v = 0,1,2,3,… q Angular frequency ω = √k⁄meff q An effective spring constant k for the bond involved q Effective mass meff

VIBRATIONAL MOLECULAR LEVELS _ CONT’D

q ½ℏω comes from quantum mechanics and represents zero-point energy q The zero point energy ½ ω implies molecule never stops vibrating - even when its in the v = 0 state q Zero point energy cannot be harvested or extracted - Still exists at absolute zero - All molecules are then in v = 0 state q Energy levels are equally spaced with separation ω q Obey selection rule ∆v = ±1

VIBRATIONAL MOLECULAR LEVELS _ CONT’D

q For diatomic molecule with mass M1 and M2 - the effective mass meff = (M1M2)⁄(M1 + M2) q Energy scale for molecular vibrations is much less than that for electronic excitations q Excitation energies correspond to IR region of the spectrum q Vibrational levels are built on electronic states – each electronic state will host the whole range of vibrational states

Vibrational excitation and de-excitation

normal mode is IR-active if the dipole moment hanges during mode motion. Overtones, combinations and differences of undamental vibrations are also possible (e.g., 2v1, +v3 etc.) A non-linear molecule of N atoms has 3N-6 normal modes of vibration; a linear molecule has 3N-5.

ν1 ν 2 ν 3

Symmetric stretch Bend (Scissoring) Asymmetric stretch

q Fundamental or normal modes

q VIBRATIONAL MOLECULAR LEVELS _ CONT’D

q ROTATIONAL MOLECULAR LEVELS

q In quantum mechanics - the rigid rotor has energy levels EJ = ħ2 ⁄ 2ℑ J(J +1) q ℑ is the moment of inertia q J is the angular momentum: J = 0,1,2,3,… q The quantity ħ2 ⁄ 2ℑ is called the rotational parameter q Moment of inertia - hence rotational parameter - can be different for each rotation axis

q ROTATIONAL MOLECULAR LEVELS _ CONT’D

q Excitation energies correspond to the microwave region q Energy scale for rotations << vibrations q Each vibrational level has rotational bands built on it q Selection rule ∆J = ±1

ROTATIONAL LEVELS

q Relative positions of transitions in the absorption spectrum of a molecule

q Q branch (ΔJ = 0) (pure vibration) q R branch (ΔJ = +1) q P branch (ΔJ = -1)

q VIBRATIONAL-ROTATIONAL TRANSITION

Electronic levels

q In molecules we have two opposing forces - the repelling force of the nuclei, and the binding force of the electrons. q If the orbit of the electrons change then the binding force will change, i.e. the net potential energy of the molecule will change. q This means that the inter-atomic distance will change q Different electronic levels will have different rotational and vibrational constants

ENERGY LEVELS

q Taking rotations, vibrations, and electronic excitation into account En,v,J = En + Ev + EJ q Complex molecules may have many vibrational modes, rotational modes, etc q The combination of these different modes leads to a “smearing” of the discrete spectrum - so that broad bumps appear rather than discrete lines

E V R T E V R T E V R T

electronic V _ vibrational rotational total energy Simple versus Complex molecules

ENERGY LEVELS _CONT’D

q Ignoring electronic excitation _ the total internal energy of a molecule i the sum of its vibrational and rotational energy. Ev,J = ħω (v + ½) + ħ2 ⁄ 2ℑ J(J +1) q The wave-number of a spectral line is given by the difference of the term values of the two states q A change in vibrational quantum number v is accompanied by a change in rotational quantum number J - according to the selection rule ΔJ = 0, ±1

ENERGY LEVELS _CONT’D

q The complete set of rotational transitions between two vibrational levels is known as a ‘band’ q A band normally consists of three separate sequences; If

• ΔJ=0 we have the Q branch
• ΔJ=1 the R branch
• ΔJ=-1 the P branch

THANK YOU